Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044571/xu2308sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044571/xu2308Isup2.hkl |
CCDC reference: 1296705
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.049
- wR factor = 0.114
- Data-to-parameter ratio = 16.0
checkCIF/PLATON results
No syntax errors found
Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1 (2) 1.71
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A mixture of N-(2-(picolinamido)phenyl)picolinamide (0.316 g, 1 mmol) and Co(NO3)2.6H2O (0.291 g, 1 mmol) was dissolved in ethanol (20 ml). The mixture was closed in a steel tomb and heated at 418 K for 4 d. Single crystals suitable for X-ray diffraction analysis were obtained after cooling to room temperature.
All H atoms were located at calculated positions with C—h = 0.93 Å and refined in riding mode with Uiso(H) = 1.2Ueq(C).
Transition metal complexes with organic ligands, possessing diverse structures and special optical and electromagnetic properties, have aroused great interest among researchers. In the title complex, each cobalt(II) ion is four-coordinated in a square-planar geometry by four N atoms from one N-(2-(picolinamido)phenyl)picolinamide molecule (Fig. 1). The Co—N bond lengths are listed in Table 1. Atom N1, N2, N3 and N4 are approximately coplanar with the central Co1 ion, the maximum deviation from the least-squares plane through all five atoms being 0.0816 (1) Å for atom N1.
π-π stacking is observed between benzene ring and N3i-pyridine [symmetry code: (i) -x, 1 - y, -z], verified by the centroid–centroid distance of 3.818 (2) Å and dihedral angle of 3.08° No strong hydrogen bonds exist in the crystal, but weak C—H···O hydrogen bonding occurs in the crystal structure (Table 2).
For the structure of a related complex, [Zn(C20H14N2O2)], see: Liu et al. (2007).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2000).
Fig. 1. The asymmetric unit of (I), showing 50% probability displacement ellipsoids. | |
Fig. 2. The packing diagram of (I), viewed along c axis, Hydrogen bonds shown as dash lines. |
[Co(C18H12N4O2)] | F(000) = 764.0 |
Mr = 375.25 | Dx = 1.645 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6407 reflections |
a = 7.052 (2) Å | θ = 2.8–27.9° |
b = 18.383 (5) Å | µ = 1.15 mm−1 |
c = 11.826 (3) Å | T = 293 K |
β = 98.827 (4)° | Block, brown |
V = 1514.8 (7) Å3 | 0.31 × 0.27 × 0.22 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 3607 independent reflections |
Radiation source: fine-focus sealed tube | 2420 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
φ and ω scans | θmax = 28.3°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −8→9 |
Tmin = 0.708, Tmax = 0.776 | k = −24→24 |
11141 measured reflections | l = −15→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0344P)2 + 2.409P] where P = (Fo2 + 2Fc2)/3 |
3607 reflections | (Δ/σ)max < 0.001 |
226 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.67 e Å−3 |
[Co(C18H12N4O2)] | V = 1514.8 (7) Å3 |
Mr = 375.25 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.052 (2) Å | µ = 1.15 mm−1 |
b = 18.383 (5) Å | T = 293 K |
c = 11.826 (3) Å | 0.31 × 0.27 × 0.22 mm |
β = 98.827 (4)° |
Bruker SMART CCD area-detector diffractometer | 3607 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 2420 reflections with I > 2σ(I) |
Tmin = 0.708, Tmax = 0.776 | Rint = 0.036 |
11141 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.58 e Å−3 |
3607 reflections | Δρmin = −0.67 e Å−3 |
226 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.1858 (5) | 0.51706 (18) | −0.1917 (3) | 0.0499 (8) | |
C2 | 0.1192 (6) | 0.5110 (2) | −0.3077 (3) | 0.0545 (9) | |
H2 | 0.0519 | 0.4698 | −0.3364 | 0.065* | |
C3 | 0.1539 (6) | 0.5673 (2) | −0.3815 (3) | 0.0573 (10) | |
H3 | 0.1084 | 0.5636 | −0.4593 | 0.069* | |
C4 | 0.2551 (6) | 0.6282 (2) | −0.3395 (3) | 0.0560 (9) | |
H4 | 0.2795 | 0.6649 | −0.3895 | 0.067* | |
C5 | 0.3209 (5) | 0.63537 (19) | −0.2233 (3) | 0.0526 (9) | |
H5 | 0.3876 | 0.6770 | −0.1957 | 0.063* | |
C6 | 0.2872 (5) | 0.58037 (18) | −0.1481 (3) | 0.0489 (9) | |
C7 | 0.0889 (5) | 0.39877 (18) | −0.1229 (3) | 0.0519 (9) | |
C8 | 0.0961 (5) | 0.35929 (18) | −0.0110 (3) | 0.0520 (9) | |
C9 | 0.0198 (5) | 0.29003 (19) | −0.0069 (4) | 0.0563 (10) | |
H9 | −0.0388 | 0.2673 | −0.0734 | 0.068* | |
C10 | 0.0321 (6) | 0.25519 (19) | 0.0976 (4) | 0.0586 (10) | |
H10 | −0.0186 | 0.2087 | 0.1019 | 0.070* | |
C11 | 0.1191 (5) | 0.28933 (19) | 0.1943 (4) | 0.0569 (10) | |
H11 | 0.1295 | 0.2664 | 0.2651 | 0.068* | |
C12 | 0.1920 (5) | 0.35912 (18) | 0.1852 (4) | 0.0537 (9) | |
H12 | 0.2512 | 0.3825 | 0.2510 | 0.064* | |
C13 | 0.4128 (5) | 0.63559 (17) | 0.0370 (3) | 0.0506 (9) | |
C14 | 0.4296 (5) | 0.61761 (18) | 0.1615 (3) | 0.0510 (9) | |
C15 | 0.4930 (6) | 0.6686 (2) | 0.2440 (3) | 0.0555 (9) | |
H15 | 0.5304 | 0.7146 | 0.2230 | 0.067* | |
C16 | 0.5007 (6) | 0.6509 (2) | 0.3582 (3) | 0.0581 (10) | |
H16 | 0.5417 | 0.6849 | 0.4149 | 0.070* | |
C17 | 0.4466 (6) | 0.5820 (2) | 0.3865 (3) | 0.0573 (10) | |
H17 | 0.4516 | 0.5685 | 0.4627 | 0.069* | |
C18 | 0.3848 (6) | 0.5335 (2) | 0.2996 (3) | 0.0538 (9) | |
H18 | 0.3484 | 0.4871 | 0.3191 | 0.065* | |
Co1 | 0.27021 (6) | 0.49353 (2) | 0.04659 (4) | 0.03724 (14) | |
N1 | 0.1613 (4) | 0.46612 (15) | −0.1059 (3) | 0.0487 (7) | |
N2 | 0.3428 (4) | 0.57967 (14) | −0.0291 (3) | 0.0477 (7) | |
N3 | 0.1795 (4) | 0.39377 (14) | 0.0844 (3) | 0.0503 (7) | |
N4 | 0.3747 (4) | 0.54978 (15) | 0.1889 (3) | 0.0502 (7) | |
O1 | 0.0223 (4) | 0.36877 (13) | −0.2134 (2) | 0.0581 (7) | |
O2 | 0.4601 (4) | 0.69679 (12) | 0.0071 (2) | 0.0561 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.058 (2) | 0.0421 (18) | 0.050 (2) | 0.0018 (15) | 0.0098 (17) | −0.0009 (15) |
C2 | 0.062 (2) | 0.050 (2) | 0.052 (2) | 0.0025 (17) | 0.0091 (18) | −0.0002 (17) |
C3 | 0.065 (3) | 0.054 (2) | 0.053 (2) | 0.0039 (18) | 0.010 (2) | 0.0036 (18) |
C4 | 0.064 (2) | 0.051 (2) | 0.054 (2) | 0.0044 (18) | 0.0116 (19) | 0.0064 (17) |
C5 | 0.061 (2) | 0.0445 (19) | 0.054 (2) | 0.0032 (16) | 0.0121 (19) | 0.0060 (16) |
C6 | 0.058 (2) | 0.0388 (17) | 0.051 (2) | 0.0018 (15) | 0.0113 (18) | 0.0032 (15) |
C7 | 0.058 (2) | 0.0372 (17) | 0.061 (2) | −0.0034 (15) | 0.0095 (19) | −0.0082 (16) |
C8 | 0.056 (2) | 0.0337 (17) | 0.067 (2) | −0.0029 (15) | 0.0128 (19) | −0.0036 (16) |
C9 | 0.060 (2) | 0.0366 (18) | 0.074 (3) | −0.0034 (16) | 0.014 (2) | −0.0023 (18) |
C10 | 0.062 (3) | 0.0384 (18) | 0.077 (3) | −0.0029 (16) | 0.015 (2) | 0.0028 (19) |
C11 | 0.062 (2) | 0.0375 (18) | 0.073 (3) | −0.0021 (16) | 0.016 (2) | 0.0071 (18) |
C12 | 0.059 (2) | 0.0354 (17) | 0.068 (2) | −0.0016 (15) | 0.0153 (19) | 0.0072 (16) |
C13 | 0.060 (2) | 0.0334 (17) | 0.058 (2) | −0.0046 (15) | 0.0104 (19) | −0.0018 (15) |
C14 | 0.061 (2) | 0.0363 (17) | 0.056 (2) | −0.0030 (15) | 0.0095 (18) | −0.0065 (15) |
C15 | 0.065 (2) | 0.0416 (19) | 0.059 (2) | −0.0029 (17) | 0.0088 (19) | −0.0092 (17) |
C16 | 0.069 (3) | 0.047 (2) | 0.058 (2) | −0.0019 (17) | 0.008 (2) | −0.0107 (17) |
C17 | 0.070 (3) | 0.048 (2) | 0.054 (2) | −0.0012 (18) | 0.009 (2) | −0.0086 (17) |
C18 | 0.067 (3) | 0.0446 (19) | 0.050 (2) | −0.0017 (17) | 0.0091 (19) | −0.0060 (16) |
Co1 | 0.0450 (3) | 0.0240 (2) | 0.0429 (2) | 0.00014 (17) | 0.00702 (18) | −0.00024 (18) |
N1 | 0.0566 (18) | 0.0376 (14) | 0.0520 (17) | −0.0022 (13) | 0.0090 (15) | −0.0046 (13) |
N2 | 0.0580 (19) | 0.0330 (14) | 0.0527 (17) | −0.0026 (12) | 0.0103 (14) | 0.0017 (12) |
N3 | 0.0558 (19) | 0.0321 (14) | 0.0643 (19) | −0.0019 (12) | 0.0137 (16) | 0.0025 (13) |
N4 | 0.0617 (19) | 0.0385 (15) | 0.0507 (18) | −0.0019 (13) | 0.0097 (15) | −0.0054 (13) |
O1 | 0.0637 (17) | 0.0441 (13) | 0.0657 (17) | −0.0042 (12) | 0.0071 (14) | −0.0120 (12) |
O2 | 0.0665 (18) | 0.0362 (13) | 0.0658 (17) | −0.0076 (11) | 0.0105 (14) | 0.0002 (11) |
C1—C2 | 1.385 (5) | C11—C12 | 1.392 (5) |
C1—N1 | 1.411 (5) | C11—H11 | 0.9300 |
C1—C6 | 1.420 (5) | C12—N3 | 1.342 (5) |
C2—C3 | 1.399 (5) | C12—H12 | 0.9300 |
C2—H2 | 0.9300 | C13—O2 | 1.240 (4) |
C3—C4 | 1.379 (5) | C13—N2 | 1.339 (4) |
C3—H3 | 0.9300 | C13—C14 | 1.496 (5) |
C4—C5 | 1.387 (5) | C14—N4 | 1.359 (4) |
C4—H4 | 0.9300 | C14—C15 | 1.377 (5) |
C5—C6 | 1.390 (5) | C15—C16 | 1.382 (5) |
C5—H5 | 0.9300 | C15—H15 | 0.9300 |
C6—N2 | 1.402 (4) | C16—C17 | 1.379 (5) |
C7—O1 | 1.231 (4) | C16—H16 | 0.9300 |
C7—N1 | 1.343 (4) | C17—C18 | 1.380 (5) |
C7—C8 | 1.503 (5) | C17—H17 | 0.9300 |
C8—N3 | 1.349 (5) | C18—N4 | 1.334 (5) |
C8—C9 | 1.386 (5) | C18—H18 | 0.9300 |
C9—C10 | 1.382 (5) | Co1—N1 | 1.916 (3) |
C9—H9 | 0.9300 | Co1—N2 | 1.926 (3) |
C10—C11 | 1.365 (5) | Co1—N3 | 2.015 (3) |
C10—H10 | 0.9300 | Co1—N4 | 2.016 (3) |
C2—C1—N1 | 126.8 (3) | O2—C13—N2 | 128.4 (3) |
C2—C1—C6 | 120.0 (3) | O2—C13—C14 | 119.8 (3) |
N1—C1—C6 | 113.2 (3) | N2—C13—C14 | 111.8 (3) |
C1—C2—C3 | 119.5 (4) | N4—C14—C15 | 122.0 (4) |
C1—C2—H2 | 120.3 | N4—C14—C13 | 117.0 (3) |
C3—C2—H2 | 120.3 | C15—C14—C13 | 121.0 (3) |
C4—C3—C2 | 120.5 (4) | C14—C15—C16 | 119.4 (4) |
C4—C3—H3 | 119.8 | C14—C15—H15 | 120.3 |
C2—C3—H3 | 119.8 | C16—C15—H15 | 120.3 |
C3—C4—C5 | 120.6 (4) | C17—C16—C15 | 118.9 (4) |
C3—C4—H4 | 119.7 | C17—C16—H16 | 120.5 |
C5—C4—H4 | 119.7 | C15—C16—H16 | 120.5 |
C4—C5—C6 | 120.0 (4) | C16—C17—C18 | 118.7 (4) |
C4—C5—H5 | 120.0 | C16—C17—H17 | 120.7 |
C6—C5—H5 | 120.0 | C18—C17—H17 | 120.7 |
C5—C6—N2 | 126.8 (3) | N4—C18—C17 | 123.3 (4) |
C5—C6—C1 | 119.3 (3) | N4—C18—H18 | 118.4 |
N2—C6—C1 | 113.8 (3) | C17—C18—H18 | 118.4 |
O1—C7—N1 | 129.0 (4) | N1—Co1—N2 | 82.85 (12) |
O1—C7—C8 | 120.4 (3) | N1—Co1—N3 | 82.80 (12) |
N1—C7—C8 | 110.7 (3) | N2—Co1—N3 | 165.31 (13) |
N3—C8—C9 | 121.6 (4) | N1—Co1—N4 | 164.37 (12) |
N3—C8—C7 | 117.5 (3) | N2—Co1—N4 | 82.93 (12) |
C9—C8—C7 | 120.9 (3) | N3—Co1—N4 | 111.67 (12) |
C10—C9—C8 | 119.1 (4) | C7—N1—C1 | 126.2 (3) |
C10—C9—H9 | 120.5 | C7—N1—Co1 | 118.2 (3) |
C8—C9—H9 | 120.5 | C1—N1—Co1 | 115.3 (2) |
C11—C10—C9 | 119.6 (3) | C13—N2—C6 | 126.9 (3) |
C11—C10—H10 | 120.2 | C13—N2—Co1 | 117.4 (2) |
C9—C10—H10 | 120.2 | C6—N2—Co1 | 114.9 (2) |
C10—C11—C12 | 118.9 (4) | C12—N3—C8 | 118.8 (3) |
C10—C11—H11 | 120.6 | C12—N3—Co1 | 130.5 (2) |
C12—C11—H11 | 120.6 | C8—N3—Co1 | 110.7 (2) |
N3—C12—C11 | 122.1 (4) | C18—N4—C14 | 117.7 (3) |
N3—C12—H12 | 119.0 | C18—N4—Co1 | 131.4 (2) |
C11—C12—H12 | 119.0 | C14—N4—Co1 | 110.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1 | 0.93 | 2.39 | 2.963 (5) | 120 |
C5—H5···O2 | 0.93 | 2.40 | 2.974 (5) | 120 |
C10—H10···O1i | 0.93 | 2.59 | 3.200 (5) | 124 |
C16—H16···O2ii | 0.93 | 2.54 | 3.344 (4) | 145 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C18H12N4O2)] |
Mr | 375.25 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.052 (2), 18.383 (5), 11.826 (3) |
β (°) | 98.827 (4) |
V (Å3) | 1514.8 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.15 |
Crystal size (mm) | 0.31 × 0.27 × 0.22 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.708, 0.776 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11141, 3607, 2420 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.114, 0.98 |
No. of reflections | 3607 |
No. of parameters | 226 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.67 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2000).
Co1—N1 | 1.916 (3) | Co1—N3 | 2.015 (3) |
Co1—N2 | 1.926 (3) | Co1—N4 | 2.016 (3) |
N1—Co1—N2 | 82.85 (12) | N1—Co1—N4 | 164.37 (12) |
N1—Co1—N3 | 82.80 (12) | N2—Co1—N4 | 82.93 (12) |
N2—Co1—N3 | 165.31 (13) | N3—Co1—N4 | 111.67 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O1 | 0.93 | 2.39 | 2.963 (5) | 120 |
C5—H5···O2 | 0.93 | 2.40 | 2.974 (5) | 120 |
C10—H10···O1i | 0.93 | 2.59 | 3.200 (5) | 124 |
C16—H16···O2ii | 0.93 | 2.54 | 3.344 (4) | 145 |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+3/2, z+1/2. |
Transition metal complexes with organic ligands, possessing diverse structures and special optical and electromagnetic properties, have aroused great interest among researchers. In the title complex, each cobalt(II) ion is four-coordinated in a square-planar geometry by four N atoms from one N-(2-(picolinamido)phenyl)picolinamide molecule (Fig. 1). The Co—N bond lengths are listed in Table 1. Atom N1, N2, N3 and N4 are approximately coplanar with the central Co1 ion, the maximum deviation from the least-squares plane through all five atoms being 0.0816 (1) Å for atom N1.
π-π stacking is observed between benzene ring and N3i-pyridine [symmetry code: (i) -x, 1 - y, -z], verified by the centroid–centroid distance of 3.818 (2) Å and dihedral angle of 3.08° No strong hydrogen bonds exist in the crystal, but weak C—H···O hydrogen bonding occurs in the crystal structure (Table 2).